US6399111B1 - Amorphous silicas and oral compositions - Google Patents
Amorphous silicas and oral compositions Download PDFInfo
- Publication number
- US6399111B1 US6399111B1 US09/395,769 US39576999A US6399111B1 US 6399111 B1 US6399111 B1 US 6399111B1 US 39576999 A US39576999 A US 39576999A US 6399111 B1 US6399111 B1 US 6399111B1
- Authority
- US
- United States
- Prior art keywords
- silica
- refractive index
- amorphous silica
- toothpaste
- rda
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 claims description 11
- 239000000606 toothpaste Substances 0.000 abstract description 30
- 229940034610 toothpaste Drugs 0.000 abstract description 25
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 description 38
- 239000003921 oil Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- -1 alkyl sulphates Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- 239000006072 paste Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000009472 formulation Methods 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 239000003082 abrasive agent Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000003906 humectant Substances 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000600 sorbitol Substances 0.000 description 5
- 235000010356 sorbitol Nutrition 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000551 dentifrice Substances 0.000 description 3
- 210000004268 dentin Anatomy 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 230000002882 anti-plaque Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 239000004150 EU approved colour Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 235000014749 Mentha crispa Nutrition 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 244000078639 Mentha spicata Species 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000008122 artificial sweetener Substances 0.000 description 1
- 235000021311 artificial sweeteners Nutrition 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004075 cariostatic agent Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000832 lactitol Substances 0.000 description 1
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 description 1
- 235000010448 lactitol Nutrition 0.000 description 1
- 229960003451 lactitol Drugs 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- JWSMTBMIGYJJJM-UHFFFAOYSA-N magnesium;azane Chemical compound N.[Mg+2] JWSMTBMIGYJJJM-UHFFFAOYSA-N 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000223 polyglycerol Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 229940045885 sodium lauroyl sarcosinate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/02—Amorphous compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Definitions
- the present invention relates to amorphous silicas particularly used as abrasives in oral compositions. More particularly, the present invention relates to amorphous precipitated silicas with good cleaning properties associated with low abrasion characteristics which are suitable for oral compositions with low refractive index. The present invention further relates to oral compositions containing such silicas.
- Toothpaste compositions are well characterised in the literature and many compositions are disclosed in patent specifications and other literature. Toothpaste compositions contain a number of specific components for example abrasive agents, fluoride sources, binders, preservatives, humectants, anti plaque agents, colouring agents, water, flavour and other optional ingredients.
- abrasive agent is required to provide the appropriate cleaning and plaque removal without subjecting the tooth itself to excessive abrasion.
- a toothpaste composition will contain from about 5% to about 50% preferably up to about 30% by weight of abrasive.
- abrasives are aluminas, calcium carbonates and calcium phosphate. More recently synthetic silicas have been adopted because of their efficient cleaning, compatibility with other ingredients and their physical properties.
- silica for use in toothpaste formulations is its oil absorption capacity. For a material with the same particle size, this property relates directly to the thickening effect obtained when adding the silica into a toothpaste formulation; the higher the oil absorption capacity the higher the observed thickening effect. Therefore the higher the oil absorption capacity, the lower the volume of silica which can be incorporated into the toothpaste composition.
- silica for use in toothpaste formulations is its ability to provide the appropriate cleaning and plaque removal without subjecting the tooth itself to excessive abrasion i.e. without damaging dentine or enamel. Normally cleaning capability is correlated with abrasion properties.
- a silica for use in transparent toothpaste formulations is its apparent refractive index.
- Any transparent toothpaste can be characterised by its refractive index.
- refractive index When incorporating an abrasive material into a transparent toothpaste it is important that this abrasive material remains invisible, i.e. that the clarity of the toothpaste remains the same. This is only achieved if the abrasive material has an apparent refractive index which matches the refractive index of the toothpaste.
- toothpastes can have refractive indices ranging from 1.430 to 1.470. A refractive index of below 1.445 is generally considered as a low refractive index.
- the RDA values therefore refer to the abrasion property of an unknown toothpaste containing an unknown amount of a specific amorphous silica and it is not possible, relying on U.S. Pat. No. 5,225,177 to know what is the RDA value of the silica.
- silicas can be broadly categorised as low abrasion if less than 90 RDA and medium abrasion if between 110-150 RDA. Samples of commercially available toothpaste silicas were submitted to Missouri Analytical Laboratories and the RDA value of the silica was determined with the following results:
- SILICA NAME RDA ZEODENT 113 84 ZEODENT 115 97 TIXOSIL 73 83 SIDENT 9 113 SIDENT 12 91 SORBOSIL AC77 125 SORBOSIL AC35 110 (NB: Zeodent, Tixosil, Sident and Sorbosil are registered trade marks of Huber, Rhone Poulenc, Degussa and Crosfield respectively.)
- the refractive index of a toothpaste is mainly governed by its humectant/water ratio, with higher ratios giving higher refractive indices.
- the humectant for example Sorbitol, is an expensive component with a high refractive index (>1.46), whereas water has a lower refractive index and is cheap.
- the oil absorption is determined by the ASTM spatula rub-out method (American Society Of Test Material Standards D, 281).
- the weight mean particle size of the silica is determined using a Malvern Mastersizer model X, with a 45 mm lens and MS15 sample presentation unit.
- This instrument made by Malvern Instruments, Malvern, Worcestershire uses the principle of Fraunhoffer diffraction, utilising a low power He/Ne laser. Before measurement the sample is dispersed ultrasonically in water for 7 minutes to form an aqueous suspension.
- the Malvern Mastersizer measures the weight particle size distribution of the silica.
- the weight mean particle size (d 50 ) or 50 percentile, the 10 percentile (d 10 ) and the 90 percentile (d 90 ) are easily obtained from the data generated by the instrument.
- Loose bulk density is determined by weighing approximately 180 ml of silica into a dry 250 ml measuring cylinder, inverting the cylinder ten times to remove air pockets and reading the final settled volume.
- Loose ⁇ ⁇ bulk ⁇ ⁇ density Weight Volume ⁇ 1000 ⁇ ⁇ g / l
- Sulphate is determined gravimetrically by hot water extraction of the silica, followed by precipitation as barium sulphate.
- Chloride is determined by hot water extraction of the silica, followed by titration with standard silver nitrate solution using potassium chromate as indicator (Mohr's method).
- Moisture loss is determined by the loss in weight of a silica when dried to constant weight in an electric oven at 105° C.
- Ignition loss is determined by the loss in weight of a silica when ignited in a furnace at 1000° C. to constant weight.
- Structural water content is defined by the difference between the ignition loss at 1000° C. and the moisture loss at 105° C.
- This measurement is carried out on a 5% w/w suspension of the silica in boiled demineralised water (CO 2 free).
- the sample of silica is dispersed in a range of Sorbitol syrup (70% Sorbitol)/water mixtures. After de-aeration, usually 1 hour, the transmission of the dispersions is determined using a spectrophotometer at 589 nm; water being used as blank. The refractive index of each dispersion is also measured using an Abbe refractometer.
- a graphical representation of transmission plotted against refractive index allows the range of refractive indices over which the transmission exceeds 70% to be determined.
- the maximum transmission of the sample and the apparent refractive index of silica at which this is obtained can also be estimated from this graph.
- the amorphous silica of the invention presents a peak of light transmission in the refractive index range of 1.430 to 1.444, most preferably between 1.436 to 1.444. This enables the silica to be incorporated into transparent oral compositions of low refractive indices.
- the amorphous silica of the invention presents a structural water content of between 3.5% and 5.0%, preferably between 4.0 and 4.5%, a BET surface area of 50 to 350 m 2 /g, preferably between 50 and 250 m 2 /g, a pH in a 5% solution of between 6 and 7.5, a loose bulk density of between 180 and 300 g/l.
- It is a second object of the present invention to provide an oral composition comprising an amorphous silica, said amorphous silica having:
- the amorphous silica is a precipitated silica having an oil absorption capacity of between 90 and 145 cm 3 /100 g, preferably between 100 and 125 cm 3 /100 g.
- the amorphous silica is the amorphous silica of the present invention.
- This toothpaste composition is capable of cleaning and polishing human teeth without damaging said teeth.
- the level of the amorphous silica may be wide ranging, for example depending upon the physical form of the desired end product.
- compositions of the invention are in the form of pastes, gels, creams or liquids, the exact physical properties of which may be controlled for example by suitable adjustment of the solid to liquid ratio and/or the viscosity of the liquid phase, e.g. by selecting appropriate contents of adjunct components, as described further below.
- the amorphous silica of the invention is present in the composition in an amount of from about 1 to about 99% by weight, more preferably from about 2 to about 60%, even more preferably from about 3 to about 40%.
- the amorphous silica of the invention is preferably present in an amount of from about 1 to about 30% by weight, more preferably from about 5 to about 25%.
- compositions of the invention may contain one or more additional components, as will now be described.
- Oral compositions of the invention preferably comprise one or more surfactants, preferably selected from anionic, nonionic, amphoteric and zwitterionic surfactants, and mixtures thereof, all being suitable for dental and/or oral use.
- surfactants preferably selected from anionic, nonionic, amphoteric and zwitterionic surfactants, and mixtures thereof, all being suitable for dental and/or oral use.
- Suitable anionic surfactants may include soaps, alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkanoyl taurates, alkyl succinates, alkyl sulphosuccinates, N-alkoyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha-olefin sulphonates, especially their sodium, magnesium ammonium and mono-, di- and triethanolamine salts.
- the alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated.
- Example of preferred anionic surfactants may include sodium lauryl sulphate, sodium dodecylbenzene sulphonate, sodium lauroyl sarcosinate and sodium coconut monoglyceride sulphonate.
- Nonionic surfactants which may be suitable for use in composition of the invention include sorbitan and polyglycerol esters of fatty acids, as well as ethylene oxide/propylene oxide block copolymers.
- Amphoteric surfactants which may be suitable for use in compositions of the invention include betaines such as cocamidopropyl betaine, and sulphobetaines, for example.
- the surfactant(s) may be present in the oral composition of the invention in a total amount of from about 0.1 to about 3% by weight.
- Water is another preferred component of the oral compositions of the invention and may be present in an amount of from about 1 to about 90% by weight, preferably from about 10 to about 60%, more preferably from about 15 to about 50% and most preferably for clear pastes from about 1 to about 20%.
- Toothpastes and creams of this invention may also contain humectants, for example polyols such as glycerol, sorbitol syrup, polyethylene glycol, lactitol, xylitol and hydrogenated corn syrup.
- humectants for example polyols such as glycerol, sorbitol syrup, polyethylene glycol, lactitol, xylitol and hydrogenated corn syrup.
- the total amount of humectant, if present, may be for example in the range of from about 10 to about 85% by weight of the composition.
- a particularly preferred means for thickening the oral compositions of the invention is by the inclusion of conventional thickening materials such as thickening silicas, examples of which have already been mentioned above.
- suspending/thickening agents include for example polyacrylic acid, copolymers and cross-linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid-containing monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, esters of ethylene glycol or esters of polyethylene glycol (e.g. fatty acid esters thereof), heteropolysaccharide gums such as xanthan and guar gums, and cellulose derivatives such as sodium carboxymethyl cellulose.
- Particularly suitable thickening agents are xanthan gum and sodium carboxymethyl cellulose.
- the thickening agent and/or suspending agent may be present in the composition in a total amount of from about 0.1 to about 50% by weight; preferably from about 0 to about 15%, most preferably from about 1 to about 10% for silica thickening agents; preferably from about 0.1to about 5% for polymer suspending agents.
- compositions of the invention may contain one or more other components conventionally found in oral compositions.
- suitable additional ingredients include: flavouring substances, e.g. peppermint, spearmint; artificial sweeteners; perfume or breath freshening substances; pearlescing agents; peroxy compounds, e.g. hydrogen peroxide or peracetic acid; opacifiers; pigments and colourings; preservatives; moisturising agents; fluoride-containing compounds; anti-caries agents; anti-plaque agents; therapeutic agents such as zinc citrate, Triclosan (ex Ciba Geigy); proteins; salts; pH adjusting agents.
- compositions in accordance with the present invention may be made by conventional methods of preparing oral compositions.
- Pastes and creams may be prepared by conventional techniques, for example using high shear mixing systems under vacuum.
- FIG. 1 represents the RIT Alphanumeric Resolution Test Object, RT 4-74, produced by Graphic Arts Research Center, Rochester Institute of Technology.
- the final slurry was then filtered and washed with water to remove excess electrolyte.
- the residual electrolyte would be less than 2% on a dry weight basis.
- the filter cake in each example was flash dried to remove the water rapidly from the silica so that the structure is maintained, and comminuted to the desired particle size range.
- the precipitated silicas obtained had the properties expressed on a dry weight basis listed in Table 2.
- amorphous silica prepared as described in example 1 was formulated at 8 and 10% loading to produce transparent toothpastes formulations.
- Example 2 Example 3 Ingredient (% w/w) (% w/w) Sorbitol 58.0 58.0 Water 14.99 13.74 Silica of the Invention 8.0 10.0 (Example 1) Sorbosil TC15 (*) 9.5 8.75 Other active ingredients to 100% to 100% Refractive index 1.4386 1.4425 Clarity number +3 +13 The RDA values of these toothpastes were less than 60. (*) Sorbosil TC15 is thickening silica produced by Crosfield ltd.
Abstract
Description
SILICA NAME | RDA | ||
ZEODENT 113 | 84 | ||
ZEODENT 115 | 97 | ||
TIXOSIL 73 | 83 | ||
SIDENT 9 | 113 | ||
SIDENT 12 | 91 | ||
SORBOSIL AC77 | 125 | ||
SORBOSIL AC35 | 110 | ||
(NB: Zeodent, Tixosil, Sident and Sorbosil are registered trade marks of Huber, Rhone Poulenc, Degussa and Crosfield respectively.) |
TABLE 1 | |||
TEST | EXAMPLE 1 | ||
Vessel Capacity (liters) | 64 | ||
Water Volume (A) (liters) | 11.9 | ||
Electrolyte (B) (grammes) | 300 | ||
Electrolyte type | Na2SO4 | ||
Silicate ratio SiO2/Na2O | 2.26 | ||
by wt. | |||
SiO2 Concn. in Silicate | 14.24 | ||
(% w/w) | |||
Silicate vol. (C) (liters) | 0.19 | ||
Silicate vol. (D) (liters) | 18.5 | ||
Acid concn. (% w/w) | 17.6 | ||
Acid I vol. (F) (liters) | 9.4 | ||
Sol Time (G) (mins.) | 40 | ||
Temperature (H) (° C.) | 88 | ||
Acid II addition time (J) | 9.5 | ||
(mins.) | |||
End of batch pH (K) | 3.5 | ||
TABLE 2 | |||
TEST | EXAMPLE 1 | ||
Silica RDA | 49 | ||
Max. % Transmission | 98 | ||
At Refractive Index of | 1.442 | ||
Oil Absorption | 120 | ||
(mls/100 g) | |||
pH | 6.2 | ||
A.p.s. (um) | 7.3 | ||
Moisture loss @ 105° C. | 4.5 | ||
Ignition Loss @ 1000° C. | 8.5 | ||
SA (m2/g) | 75 | ||
SO4= (%) | 0.1 | ||
Cl− (%) | 0.01 | ||
Loose Bulk Density (g/l) | 285 | ||
Example 2 | Example 3 | |||
Ingredient | (% w/w) | (% w/w) | ||
Sorbitol | 58.0 | 58.0 | ||
Water | 14.99 | 13.74 | ||
Silica of the Invention | 8.0 | 10.0 | ||
(Example 1) | ||||
Sorbosil TC15 (*) | 9.5 | 8.75 | ||
Other active ingredients | to 100% | to 100% | ||
Refractive index | 1.4386 | 1.4425 | ||
Clarity number | +3 | +13 | ||
The RDA values of these toothpastes were less than 60. | ||||
(*) Sorbosil TC15 is thickening silica produced by Crosfield ltd. |
Claims (10)
Priority Applications (1)
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US09/395,769 US6399111B1 (en) | 1996-01-19 | 1999-09-14 | Amorphous silicas and oral compositions |
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GB9601084 | 1996-01-19 | ||
GBGB9601084.8A GB9601084D0 (en) | 1996-01-19 | 1996-01-19 | Amorphous silicas and oral compositions |
US78603697A | 1997-01-21 | 1997-01-21 | |
US09/395,769 US6399111B1 (en) | 1996-01-19 | 1999-09-14 | Amorphous silicas and oral compositions |
Related Parent Applications (1)
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US78603697A Continuation | 1996-01-19 | 1997-01-21 |
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US09/395,769 Expired - Fee Related US6399111B1 (en) | 1996-01-19 | 1999-09-14 | Amorphous silicas and oral compositions |
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US (1) | US6399111B1 (en) |
EP (1) | EP0785169B2 (en) |
CN (1) | CN1269731C (en) |
AT (1) | ATE221858T1 (en) |
AU (1) | AU706805B2 (en) |
BR (1) | BR9700718A (en) |
DE (1) | DE69714485T3 (en) |
ES (1) | ES2181856T5 (en) |
GB (1) | GB9601084D0 (en) |
ZA (1) | ZA97357B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6521214B1 (en) * | 1996-07-05 | 2003-02-18 | Rhone-Poulenc Chimie | Process for preparation of abrasive precipitated silica |
WO2003050041A1 (en) * | 2001-12-10 | 2003-06-19 | J.M. Huber Corporation | Precipitated silicas suitable for transparent dentrifices |
US20030131536A1 (en) * | 2001-12-21 | 2003-07-17 | Kostinko John A. | Precipitated silica |
WO2004043419A1 (en) * | 2002-11-13 | 2004-05-27 | J.M. Huber Corporation | Abrasive compositions for clear toothpaste |
WO2005065634A1 (en) * | 2004-01-09 | 2005-07-21 | Ineos Silicas Limited | Dental abrasive system |
US20060008422A1 (en) * | 2004-01-09 | 2006-01-12 | Abraham Araya | Dentifrice compositons and abrasive systems |
US7008617B1 (en) * | 2001-12-10 | 2006-03-07 | J.M. Huber Corporation | Precipitated silicas |
US20070292458A1 (en) * | 2004-01-09 | 2007-12-20 | Ineos Silicas Limited | Dentifrice Compositions Containing Zeolites |
US20090010973A1 (en) * | 2005-12-14 | 2009-01-08 | Ineos Silicas Limited | Silicas |
EP2720756A2 (en) * | 2011-06-17 | 2014-04-23 | Colgate-Palmolive Company | Oral care compositions |
WO2014196592A1 (en) * | 2013-06-07 | 2014-12-11 | サンスター スイス エスエー | Oral composition containing diamond particles |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL172190B1 (en) † | 1992-10-28 | 1997-08-29 | Crosfield Joseph & Sons | Silicates |
GB9601084D0 (en) † | 1996-01-19 | 1996-03-20 | Unilever Plc | Amorphous silicas and oral compositions |
US6419174B1 (en) | 2000-08-18 | 2002-07-16 | J. M. Huber Corporation | Abrasive compositions and methods for making same |
US6652611B1 (en) | 2000-08-18 | 2003-11-25 | J. M. Huber Corporation | Method for making abrasive compositions and products thereof |
US6403059B1 (en) * | 2000-08-18 | 2002-06-11 | J. M. Huber Corporation | Methods of making dentifrice compositions and products thereof |
DE102011080893A1 (en) * | 2011-08-12 | 2013-02-14 | Henkel Ag & Co. Kgaa | Oral and dental care and cleaning products for sensitive teeth |
US20240099947A1 (en) | 2020-12-11 | 2024-03-28 | Pq Silicas Uk Limited | Abrasive Silica Particles |
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GB9601084D0 (en) † | 1996-01-19 | 1996-03-20 | Unilever Plc | Amorphous silicas and oral compositions |
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1996
- 1996-01-19 GB GBGB9601084.8A patent/GB9601084D0/en active Pending
- 1996-12-19 AU AU76425/96A patent/AU706805B2/en not_active Ceased
-
1997
- 1997-01-10 EP EP96309089A patent/EP0785169B2/en not_active Expired - Lifetime
- 1997-01-10 ES ES96309089T patent/ES2181856T5/en not_active Expired - Lifetime
- 1997-01-10 AT AT96309089T patent/ATE221858T1/en not_active IP Right Cessation
- 1997-01-10 DE DE69714485T patent/DE69714485T3/en not_active Expired - Fee Related
- 1997-01-16 ZA ZA97357A patent/ZA97357B/en unknown
- 1997-01-17 BR BR9700718A patent/BR9700718A/en not_active IP Right Cessation
- 1997-01-18 CN CNB97102989XA patent/CN1269731C/en not_active Expired - Fee Related
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GB2146317A (en) | 1983-03-04 | 1985-04-17 | Taki Chemical | Silica base for dentifrice and process for its preparation |
EP0227334A2 (en) | 1985-12-03 | 1987-07-01 | Unilever Plc | Precipitated silicas |
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Cited By (16)
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US6521214B1 (en) * | 1996-07-05 | 2003-02-18 | Rhone-Poulenc Chimie | Process for preparation of abrasive precipitated silica |
US7008617B1 (en) * | 2001-12-10 | 2006-03-07 | J.M. Huber Corporation | Precipitated silicas |
WO2003050041A1 (en) * | 2001-12-10 | 2003-06-19 | J.M. Huber Corporation | Precipitated silicas suitable for transparent dentrifices |
US6616916B1 (en) * | 2001-12-10 | 2003-09-09 | J. M. Huber Corporation | Transparent dentifrices |
AU2002343639B2 (en) * | 2001-12-10 | 2007-05-24 | J.M. Huber Corporation | Precipitated silicas suitable for transparent dentrifices |
US20030131536A1 (en) * | 2001-12-21 | 2003-07-17 | Kostinko John A. | Precipitated silica |
WO2004043419A1 (en) * | 2002-11-13 | 2004-05-27 | J.M. Huber Corporation | Abrasive compositions for clear toothpaste |
US20060008422A1 (en) * | 2004-01-09 | 2006-01-12 | Abraham Araya | Dentifrice compositons and abrasive systems |
WO2005065634A1 (en) * | 2004-01-09 | 2005-07-21 | Ineos Silicas Limited | Dental abrasive system |
US20070292458A1 (en) * | 2004-01-09 | 2007-12-20 | Ineos Silicas Limited | Dentifrice Compositions Containing Zeolites |
US20090010973A1 (en) * | 2005-12-14 | 2009-01-08 | Ineos Silicas Limited | Silicas |
US9968802B2 (en) * | 2005-12-14 | 2018-05-15 | Pq Silicas Uk Limited | Silicas |
EP2720756A2 (en) * | 2011-06-17 | 2014-04-23 | Colgate-Palmolive Company | Oral care compositions |
RU2577301C2 (en) * | 2011-06-17 | 2016-03-10 | Колгейт-Палмолив Компани | Compositions for oral cavity care |
WO2014196592A1 (en) * | 2013-06-07 | 2014-12-11 | サンスター スイス エスエー | Oral composition containing diamond particles |
JPWO2014196592A1 (en) * | 2013-06-07 | 2017-02-23 | サンスター スイス エスエー | Oral composition containing diamond particles |
Also Published As
Publication number | Publication date |
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ATE221858T1 (en) | 2002-08-15 |
DE69714485T3 (en) | 2007-10-31 |
ZA97357B (en) | 1998-07-16 |
CN1269731C (en) | 2006-08-16 |
EP0785169A1 (en) | 1997-07-23 |
EP0785169B1 (en) | 2002-08-07 |
CN1165647A (en) | 1997-11-26 |
EP0785169B2 (en) | 2006-10-11 |
BR9700718A (en) | 1998-10-06 |
GB9601084D0 (en) | 1996-03-20 |
DE69714485T2 (en) | 2002-12-19 |
MX9700482A (en) | 1998-05-31 |
AU7642596A (en) | 1997-07-24 |
AU706805B2 (en) | 1999-06-24 |
ES2181856T5 (en) | 2007-05-01 |
DE69714485D1 (en) | 2002-09-12 |
ES2181856T3 (en) | 2003-03-01 |
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